Hydrotreating catalyst with a titanium containing carrier and organic additive

ABSTRACT

Disclosed is a catalyst for use in hydrotreating hydrocarbon feedstocks and methods of making the same catalyst. Specifically, a catalyst is disclosed comprises at least one Group VIB metal component, at least one Group VIII metal component, an organic additive resulting in a C-content of the final catalysts of about 1 to about 30 wt % C, and preferably about 1 to about 20 wt % C, and more preferably about 5 to about 15 wt % C and a titanium-containing carrier component, wherein the amount of the titanium component is in the range of about 3 to about 60 wt %, expressed as an oxide (TiO 2 ) and based on the total weight of the catalyst. The titanium-containing carrier is formed by co-extruding or precipitating a titanium source with a AI 2 O 3  precursor to form a porous support material primarily comprising AI 2 O 3  or by impregnating a titanium source onto a porous support material primarily comprising AI 2 O 3 . Special preference is given to alumina and alumina containing up to and no more than 1 wt % of silica, preferably no more than 0.5 wt % based on the total weight of the support (dry base).

TECHNICAL FIELD

The present invention is in the field of catalysts useful forhydrotreating hydrocarbon feedstocks in refining processes.

THE INVENTION

In general, hydrotreating catalysts are composed of a carrier havingdeposited thereon a Group VIB (of the Periodic Table) metal componentand a Group VIII (of the Periodic Table) metal component. The mostcommonly employed Group VIB metals are molybdenum and tungsten, whilecobalt and nickel are the conventional Group VIII metals. Phosphorus mayalso be present in the catalyst. The prior art processes for preparingthese catalysts are characterized in that a carrier material iscomposited with hydrogenation or hydrotreating metal components, forexample by impregnation, after which the composite is generally calcinedto convert the metal components into their oxides. Before being used inhydrotreating, the catalysts are generally sulfided to convert thehydrogenation metals into their sulfides. Processes for activating andregenerating such catalysts are also known.

The use of TiO₂-containing carriers in hydroprocessing catalysts, whichare generally calcined after application of the active metals, is widelyknown. The inclusion of TiO₂ in the hydroprocessing carriers hascommonly been reported to show higher desulfurization activity, but thefundamentals behind such behavior are not well understood. For example,US Patent Publications US20120181219 and US20130153467 disclose a metalcomponent selected from Groups VIA and VIII in the periodic table,supported on a silica-titania-alumina support where the total of thediffraction peak area indicating the crystal structure of anatasetitania (101) planes and the diffraction peak area indicating thecrystal structure of rutile titania (110) planes is ¼ or less of thediffraction peak area indicating the aluminum crystal structure ascribedto γ-alumina (400) planes, as measured by X-ray diffraction analysis.However, these references fail to disclose the combination of thepresent invention, (i.e. the combination of a TiO₂ containing supportand the use of an organic additive) and require the addition of silicain the carrier.

Another example is U.S. Pat. No. 6,383,975 which discloses a catalystthat uses a support consisting on an alumina matrix, having dispersed onits surface or in its mass, or in both, a metal oxide from group IVB ofthe periodic table. The support is prepared by co-precipitationtechnique, co-gelification or impregnation of the alumina with a Ticompound, soluble in an organic solvent, followed by drying at 100 to200° C. and calcination at 400 to 600° C., on oxidizing atmosphere.However, this reference also fails to disclose the combination of thepresent invention as it does not disclose the synergistic effect oftitanium and organic additives

Another example is U.S. Pat. No. 9,463,452 which discloses a catalystthat uses a titania coated alumina particles shaped into extrudates. Thehydrotreating catalyst then supports a periodic table group 6 metalcompound, a periodic table group 8-10 metal compound, a phosphoruscompound, and a saccharide. The invention of the '452 patent is limitedto a very specific manufacturing process and only to the use ofsaccharides as potential additives.

It was found that by using TiO₂-containing carriers in combination withthe use of certain organics in the preparation method, highly activehydrotreating catalysts can be made. The activity of these catalysts ishigher than (i) what can be achieved on a conventional Al₂O₃ supportwith the same organic or (ii) when the TiO₂-containing catalysts arebeing prepared without organics. Moreover, it appears the activity ofthe active phase in the catalyst prepared with TiO₂-containing supportsin combination with organics is higher than can be expected based on theeffect of the individual contributions of these parameters. This higheractive phase activity can be applied to generate hydrotreating catalystswith a superior volumetric activity or catalysts with high activity atconsiderably lower concentrations of the active Group VIB and Group VIIImetal components.

Thus, in one embodiment of the invention there is provided a catalystcomprising at least one Group VIB metal component, at least one GroupVIII metal component, an organic additive resulting in a C-content ofthe final catalysts of about 1 to about 30 wt % C, and preferably about1 to about 20 wt % C, and more preferably about 5 to about 15 wt % C anda titanium-containing carrier component, wherein the amount of thetitanium component is in the range of about 3 to about 60 wt %,expressed as an oxide (TiO₂) and based on the total weight of thecatalyst. The titanium-containing carrier is formed by co-extruding orprecipitating a titanium source with a Al₂O₃ precursor to form a poroussupport material primarily comprising Al₂O₃ or by impregnating atitanium source onto a porous support material primarily comprisingAl₂O₃.

In another embodiment of the invention, provided is a method ofproducing a catalyst. The method comprises the preparation of aTi-containing porous support material primarily comprising Al₂O₃. Thiscan be achieved by co-extruding or precipitating a titanium source witha Al₂O₃ precursor, shaping to form carrier extrudates, followed bydrying and calcination. Alternatively, porous Al₂O₃ extrudates may beimpregnated with a Ti-source followed by drying and calcination. TheTi-containing porous support is impregnated with a solution comprised ofat least one Group VIB metal source and/or at least one Group VIII metalsource. An organic additive is added in the production process either byco-impregnation with the metal sources or via a post-impregnation. Inthe process, the amount of the titanium source is sufficient so as toform a catalyst composition at least having a titanium content in therange of about 3 wt % to about 60 wt %, expressed as an oxide (TiO₂) andbased on the total weight of the catalyst after calcination.

In another embodiment of the invention, there is provided a catalystcomposition formed by the just above-described process. Anotherembodiment of the invention is a hydrotreating process carried outemploying the catalyst composition.

These and still other embodiments, advantages and features of thepresent invention shall become further apparent from the followingdetailed description, including the appended claims.

DETAILED DESCRIPTION OF THE DRAWINGS

FIG. 1 details the XRD patterns of the catalysts of the presentinvention and comparative.

Further Detailed Description of the Invention

Unless otherwise indicated, weight percent (_wt. %) as used herein isthe weight percent of the specified form of the substance, based uponthe total weight of the product for which the specified substance orform of substance is a constituent or component. The weight percent ofTiO₂ and Group VIB and Group VIII metals-oxides are based on the totalweight of the final catalyst after calcination, i.e. excluding thepresence of organics and/or water. The weight percent of organics in thefinal catalyst is based on the total weight of the final catalystwithout calcination. It should further be understood that, whendescribing steps or components or elements as being preferred in somemanner herein, they are preferred as of the initial date of thisdisclosure, and that such preference(s) could of course vary dependingupon a given circumstance or future development in the art.

The Group VIB metal component in catalysts of the invention is selectedfrom the group consisting of molybdenum, tungsten, chromium and amixture of two or more of the foregoing, while molybdenum and/ortungsten is typically preferred, and molybdenum is typically morepreferred. The Group VIII metal component is selected from groupconsisting of iron, cobalt and nickel, while nickel and/or cobalt aretypically preferred. Preferred mixtures of metals include a combinationof (a) nickel and/or cobalt and (b) molybdenum and/or tungsten. Whenhydrodesulfurization (sometimes hereafter referred to as “HDS”) activityof the catalyst is important, a combination of cobalt and molybdenum isadvantageous and typically preferred. When hydrodenitrogenation(sometimes hereafter referred to as “HDN”) activity of the catalyst isimportant, a combination of nickel and either molybdenum or tungsten isadvantageous and typically preferred.

The Group VIB metal component can be introduced as an oxide, an oxoacid, or an ammonium salt of an oxo or polyoxo anion. The Group VIBmetal compounds are formally in the +6 oxidation state. Oxides and oxoacids are preferred Group VIB metal compounds. Suitable Group VIB metalcompounds in the practice of this invention include chromium trioxide,chromic acid, ammonium chromate, ammonium dichromate, molybdenumtrioxide, molybdic acid, ammonium molybdate, ammonium para-molybdate,tungsten trioxide, tungstic acid, ammonium tungsten oxide, ammoniummetatungstate hydrate, ammonium para-tungstate, and the like. PreferredGroup VIB metal compounds include molybdenum trioxide, molybdic acid,tungstic acid and tungsten trioxide. Mixtures of any two or more GroupVIB metal compounds can be used; a mixture of products will be obtainedwhen compounds having different Group VIB metal are used. The amount ofGroup VIB metal compound employed in the catalyst will typically be inthe range of about 15 to about 30 wt % (as trioxide), based on the totalweight of the catalyst.

The Group VIII metal component is usually introduced as an oxide,hydroxide or salt. Suitable Group VIII metal compounds include, but arenot limited to, cobalt oxide, cobalt hydroxide, cobalt nitrate, cobaltcarbonate, cobalt hydroxy-carbonate, cobalt acetate, cobalt citrate,nickel oxide, nickel hydroxide, nickel nitrate, nickel carbonate, nickelhydroxy-carbonate, nickel acetate, and nickel citrate. Preferred GroupVIII metal compounds include cobalt carbonate, cobalt hydroxy-carbonate,cobalt hydroxide, nickel hydroxy-carbonate nickel carbonate and nickelhydroxide. Mixtures of two or more Group VIII metal compounds can beused; when the Group VIII metals of the compounds in the mixture aredifferent, a mixture of products will be obtained. The amount of GroupVIII metal compound employed in the catalyst will typically be in therange of about 2 to about 8 wt % (as oxide), based on the total weightof the catalyst. In a preferred embodiment of this invention, the amountof Group VIII metal compound is in the range of about 2 to about 6 wt %(as oxide), based on the total weight of the catalyst.

The titanium component will typically be introduced as titania, titanylsulfate, titanium sulfate, Titanium(IV)bis(ammonium lactato)dihydroxide,titanium alkoxide (like Ti-isopropoxide, Ti-butoxide, Ti-ethoxide,etc.), or TiCl₄. The amount of the titanium component in the catalystwill typically be in the range of about 3 to about 60 wt %, expressed asan oxide (TiO₂) and based on the total weight of the catalyst. In apreferred embodiment of this invention, the amount of titanium componentis in the range of about 5 wt % to about wt %, expressed as an oxide(TiO₂) and based on the total weight of the catalyst.

The catalyst carrier may further comprise alumina in any of the knownforms, such as gamma-alumina, eta-alumina or alpha alumina. Silica isoften applied in small amounts to serve as in the precipitation of thealumina precursor. This component may therefore be present in the finalcatalysts of the invention. Special preference is given to alumina andalumina containing up to and no more than 1 wt % of silica, preferablyno more than 0.5 wt % based on the total weight of the catalyst.

The physical properties of the final carrier are not critical to theprocess according to the invention, since the synergistic effect betweenthe use of titania containing carriers and organics should be alwaysobserved. However, it is known that there is a specific range of poresize, surface area and pore volume that performs better depending on thehydroprocessing application. All physical properties are measured vianitrogen physisorption techniques (Quadrasorb equipment and 300° C.pretreatment overnight under vacuum).

The carrier's pore volume (measured at 100 nm assuming de Boer andKelvin equations to convert relative pressure into pore diameter), willgenerally be in the range of 0.2 to 2 ml/g, preferably 0.4 to 1 ml/g.The carrier specific surface area will generally be in the range of 50to 400 m²/g (measured using the BET method). Preferably, the carrierwill have a median pore diameter in the range of 5 to 15 nm.

The catalyst is employed in the conventional manner in the form of, forexample, spheres or extrudates. Examples of suitable types of extrudateshave been disclosed in the literature (see, e.g. U.S. Pat. No.4,028,227).

The titanium compound can be incorporated into the carrier byimpregnation, co-extrusion or precipitation, atomic layer deposition(ALD), or chemical vapor deposition (CVD). It is preferred that thetitanium component is precipitated with the other components of thecarrier, as it is believed, without being bound to theory, thatprecipitation results in a better dispersion of the titanium componentemployed in the highly active catalyst of this invention than what canbe achieved via co-extrusion. Furthermore, the addition of the titaniumcomponent in this step prevents the need for an additional productionstep, as is the case when impregnation, ALD or CVD are used.

When adding the titanium via co-precipitation, known methods ofco-precipitation can be used. In particular, Aluminum sulfate (Alum) andTitanyl sulfate (TiOSO₄) or titanium sulfate can be mixed in one streamand sodium aluminate (Natal) are dosed either simultaneously orsubsequently to a heel of water at elevated T and a pH>7. Thecompositions and flow rates of Natal and Alum/TiOSO₄/titanium sulfatecan be adjusted to achieve the desired final TiO₂ content in the thuscreated TiO₂/Al₂O₃ material. The pH can be controlled constantly withNaOH or H₂SO₄. Total dosing time can be varied between minutes and 2hours and the final solid concentration in the reactor will beapproximately 2-10% on weight basis. In a subsequent step, the pH can beraised with NaOH or Natal to 9-12 to age. The slurry is then filteredand washed. The thus obtained solid can then be shaped into supportbodies via extrusion, pelletizing or pressing which can be preceded bydrying, spray-drying, milling, kneading and other methods known in theart to arrive at an extrudable material.

Strike-precipitation is very similar to co-precipitation processes, butthe acidic stream is added to the basic components dispersed in thereactor vessel. Natal is diluted in water and under vigorous stirringwaterglass is added while heating at 60° C. To this mixture aluminumsulfate and titanyl sulfate are added in 20 min with a final pH of 6.5.pH is not controlled during the addition and only allow to settle withthe complete dossing of both streams. NaOH is used to adjust the pH to7.2 and the mixture is aged for 1 hour at 60° C. while stirring. Thecake is re-slurried with water, brought to pH 10 with ammonia and agedat 95° C. for 1 hour while stirring. Then, the slurry is filtered andwashed with water to remove excess ammonia. The obtained solid can thenbe shaped into support bodies via extrusion, pelletizing or pressingwhich can be preceded by drying, spray-drying, milling, kneading andother methods known in the art to arrive at an extrudable material.

Step-precipitation can be carried out by reaction or precipitation of aTi-precursor such as titanyl sulfate on a slurry of boehmite orpseudo-boehmite in water. Firstly alumina is precipitated viasimultaneous dosing of sodium aluminate (Natal) and aluminum sulfate(Alum) to a heel of water at elevated T and a pH>7. The flows of Nataland Alum can be adjusted and the pH is controlled with NaOH or H₂SO₄.After aging at pH 9-12, filtration and washing, the thus-formed boehmiteor pseudo-boehmite filter cake can be re-slurried in water. To thisslurry TiOSO₄ or titanium sulfate can be added either simultaneously orsubsequently with NaOH at elevated T and pH>7 in about 10 minutes to 1hour. The slurry is then filtered and washed. The thus-obtained solidcan then be shaped into support bodies via extrusion pelletizing orpressing, which can be preceded by drying, spray-drying, milling,kneading and other methods known in the art to arrive at an extrudablematerial.

Co-extrusion is carried out by adding the titanium component to analumina precursor component during a kneading or mixing step. The momentof addition is not fixed. The titanium component is added as a solid oras a solution of molecular Ti-compounds. During the kneading or mixingstep, the mix is heated to a desired temperature to remove any excess ofsolvent/water if needed. Kneading or mixing is finished when the desiredmoisture content (as determined by Loss on Ignition at a temperature inthe range of 500-600° C.) is reached. Next, the mix is shaped toextrudates by using a suitable shaping technique. Besides extrusion,shaping can be accomplished via pelletizing or pressing.

The support bodies formed via precipitation and co-extrusion methods arethen dried at a temperature in the range of 80-200° C. to remove asubstantial amount of solvent/water and then calcined under air or inertconditions with or without steam at a temperature in the range of400-900° C., resulting in the case of alumina, in a carrier containing atransition alumina e.g., a gamma, theta or eta-alumina. The titaniacomponent will also be present as an oxide, such as anatase or rutile.The calcination can be in a static or rotating mode.

When adding the titanium via impregnation, the titanium precursor isapplied to a porous carrier, primarily comprising Al₂O₃. Known methodsof impregnation can be used. In particular, pore volume impregnation ispreferred. A solution of aqueous titania precursor, such as titanylsulfate, titanium sulfate or Titanium(IV)bis(ammoniumlactato)dihydroxide is prepared. Alternatively, a non-aqueous solutionof an alkoxide titantia can be prepared. Then, the alumina extrudate iscoated/impregnated with the titanium solution. The impregnated carrierso formed is then dried at a temperature in the range of 80-200° C. toremove a substantial amount of solvent/water and then generally calcinedunder air or inert conditions with or without steam at a temperature inthe range of 400-700° C.

In preparation of the TiO₂ containing support material it may beadvantageous that part of the TiO₂ is introduced in one step, whileanother part of the TiO₂ is introduced in another step.

The calcined extrudates primarily comprising Al₂O₃ and TiO₂ are thenimpregnated with a solution comprising a Group VIB metal source and/or aGroup VIII metal source and optionally a phosphorous source.Impregnation is carried out by pore volume impregnation with animpregnation solution that can also comprise the selected organicadditives in an appropriate solvent. The solvent used in preparing theadditive impregnation solution is generally water, although othercomponents such as methanol, ethanol and other alcohols may also besuitable. Impregnation can be carried out at room temperature or atelevated temperatures, but will typically be carried out at about20-100° C. Instead of impregnating techniques, dipping methods, sprayingmethods, etc. can be used. After impregnation, an optional drying stepis carried out with the objective to remove water, but leave (thelargest part) of the organic additive on the catalyst. Drying istypically carried out at a temperature in the range of 25-220° C. Incase the organics are not added in the impregnation solution containingthe metal-precursors, a subsequent impregnation step is carried out.

The final catalyst further comprises an organic additive. This organicadditive can be added together with the Group VIB metal source and/or aGroup VIII metal source or in a separate step. The organic additive isadded in amount of about 1 to about 30 wt % C, and preferably about 1 toabout 20 wt % C, and more preferably about 5 to about 15 wt % C byweight of the final catalyst. Such organic additives include an organiccompound selected from the group consisting of compounds comprising atleast two oxygen atoms and 2-carbon atoms and the compounds built upfrom these compounds. The organic compound preferably is selected fromthe group of compounds comprising at least two oxygen-containingmoieties, such as a carboxyl, carbonyl or hydroxyl moiety, and 2-10carbon atoms, and the compounds built up from these compounds. Thelatter may be, e.g., the ether, ester, acetal, acid chloride, acidamide, oligomer or polymer of this organic compound. Examples ofsuitable organic compounds include citric acid, tartaric acid, oxalicacid, malonic acid, malic acid, butanediol, pyruvic aldehyde, glycolaldehyde, and acetaldol. Organic compounds selected from the group ofcompounds comprising at least two hydroxyl groups and 2-10 carbon atomsper molecule and the compounds built up from these compounds are alsopreferred. These include, e.g., gluconic acid, tartaric acid, oraliphatic alcohols such as ethylene glycol, propylene glycol, glycerin,trimethylol ethane, trimethylol propane, etc. Compounds built up fromthese organic compounds include oligo- and polymers, e.g., diethyleneglycol, dipropylene glycol, trimethylene glycol, triethylene glycol,tributylene glycol, tetraethylene glycol, tetrapentylene glycol. Thisrange can be extrapolated to include, e.g., polyethers like polyethyleneglycol. For this last compound, polyethylene glycol with a molecularweight between 200 and 8,000 is preferred. Other compounds built up fromthese organic compounds are, e.g., ethers such as ethylene glycolmonobutyl ether, diethylene glycol monomethyl ether, diethylene glycolmonoethyl ether, diethylene glycol monopropyl ether, and diethyleneglycol monobutyl ether. Preferred organic compounds are, int. al.,ethylene glycol, diethylene glycol, polyethylene glycol, or mixturesthereof. Another group of organic compounds comprising at least twohydroxyl groups and 2-10 carbon atoms per molecule is formed by, e.g.,monosaccharides such as glucose and fructose.

The organic additive may also be a sulfur-containing organic compound.The sulfur-containing organic compound is a mercapto-carboxylic acid offormula HS—R—COOH, where R is a linear or branched, and saturated orunsaturated carbon backbone (C₁-C₁₁ with or without hetero atoms such asnitrogen) with optionally a nitrogen-containing functional group such asamine, amide, etc. Suitable examples of such mercapto-carboxylic acidinclude, but are not limited to, thioglycolic acid, thiolactic acid,thiopropionic acid, mercapto succinic acid, and cysteine.

The metals, additional phosphorus, and the organic additive can beintroduced onto the extrudates in one or more steps. The solutions usedmay or may not be heated.

In the practice of this invention, the impregnation solution mayoptionally include a phosphorus component. The phosphorous component isa compound which is typically a water soluble, acidic phosphoruscompound, particularly an oxygenated inorganic phosphorus-containingacid. Examples of suitable phosphorus compounds include metaphosphoricacid, pyrophosphoric acid, phosphorous acid, orthophosphoric acid,triphosphoric acid, tetraphosphoric acid, and precursors of acids ofphosphorus, such as ammonium hydrogen phosphates (mono-ammoniumdi-hydrogen phosphate, di-ammonium mono-hydrogen phosphate, tri-ammoniumphosphate). Mixtures of two or more phosphorus compounds can be used.The phosphorus compound may be used in liquid or solid form. A preferredphosphorus compound is orthophosphoric acid (H₃PO₄) or an ammoniumhydrogen phosphate, preferably in aqueous solution. The amount ofphosphorus compound employed in the catalyst will preferably be at leastabout 1 wt. % (as oxide P₂O₅), based on the total weight of the catalystand more preferably in the range of about 1 to about 8 wt. % (as oxideP₂O₅), based on the total weight of the catalyst.

Optionally, catalysts of the invention may be subjected to a sulfidationstep (treatment) to convert the metal components to their sulfides. Inthe context of the present specification, the phrases “sulfiding step”and “sulfidation step” are meant to include any process step in which asulfur-containing compound is added to the catalyst composition and inwhich at least a portion of the hydrogenation metal components presentin the catalyst is converted into the sulfidic form, either directly orafter an activation treatment with hydrogen. Suitable sulfidationprocesses are known in the art. The sulfidation step can take place exsitu to the reactor in which the catalyst is to be used in hydrotreatinghydrocarbon feeds, in situ, or in a combination of ex situ and in situto the reactor.

Ex situ sulfidation processes take place outside the reactor in whichthe catalyst is to be used in hydrotreating hydrocarbon feeds. In such aprocess, the catalyst is contacted with a sulfur compound, e.g., apolysulfide or elemental sulfur, outside the reactor and, if necessary,dried. In a second step, the material is treated with hydrogen gas atelevated temperature in the reactor, optionally in the presence of afeed, to activate the catalyst, i.e., to bring the catalyst into thesulfided state.

In situ sulfidation processes take place in the reactor in which thecatalyst is to be used in hydrotreating hydrocarbon feeds. Here, thecatalyst is contacted in the reactor at elevated temperature with ahydrogen gas stream mixed with a sulfiding agent, such as hydrogensulfide or a compound which under the prevailing conditions isdecomposable into hydrogen sulfide. It is also possible to use ahydrogen gas stream combined with a hydrocarbon feed comprising a sulfurcompound which under the prevailing conditions is decomposable intohydrogen sulfide. In the latter case, it is possible to sulfide thecatalyst by contacting it with a hydrocarbon feed comprising an addedsulfiding agent (spiked hydrocarbon feed), and it is also possible touse a sulfur-containing hydrocarbon feed without any added sulfidingagent, since the sulfur components present in the feed will be convertedinto hydrogen sulfide in the presence of the catalyst. Combinations ofthe various sulfiding techniques may also be applied. The use of aspiked hydrocarbon feed may be preferred.

Regardless of the approach (ex situ vs in situ), catalysts described inthis invention can be activated using the conventional start-uptechniques known in the art. Typically, the catalyst is contacted in thereactor at elevated temperature with a hydrogen gas stream mixed with asulfiding agent, such as hydrogen sulfide or a compound which under theprevailing conditions is decomposable into hydrogen sulfide. It is alsopossible to use a sulfur-containing hydrocarbon feed, without any addedsulfiding agent, since the sulfur components present in the feed will beconverted into hydrogen sulfide in the presence of the catalyst.

The catalyst compositions of this invention are those produced by theabove-described process, whether or not the process included an optionalsulfiding step.

The formed catalyst product of this invention is suitable for use inhydrotreating, hydrodenitrogenation and/or hydrodesulfurization (alsocollectively referred to herein as “hydrotreating”) of hydrocarbon feedstocks when contacted by the catalyst under hydrotreating conditions.Such hydrotreating conditions are temperatures in the range of 250-450°C., pressure in the range of 5-250 bar, liquid space velocities in therange of 0.1-10 liter/hour and hydrogen/oil ratios in the range of50-2000 Nl/l. Examples of suitable hydrocarbon feeds to be so treatedvary widely, and include middle distillates, kero, naphtha, vacuum gasoils, heavy gas oils, and the like.

The following describes experimental preparation of the support and thecatalyst, as well as use of the catalyst in hydrotreating a hydrocarbonfeedstock to illustrate activity of the catalysts so formed. Thisinformation is illustrative only, and is not intend to limit theinvention in any way.

EXAMPLES

Activity Test

The activity tests were carried out in a micro flow reactor. Light GasOil (LGO) spiked with dimethyl disulfide (DMDS) (total S content of 2.5wt %) was used for presulfiding. A Straight-run Gas Oil (SRGO), having aS content of 1.4-1.1 wt. % and a N content of 240-200 ppm, was used formedium pressure ULSD testing in Examples A-F. A Vacuum Gas Oil (VGO)feed with S content of 2.1 wt. % S and 1760 ppmN was used for HC-PTtesting in Example G. Catalysts were evaluated at equal volume, unlessstated otherwise. The relative volumetric activities for the variouscatalysts were determined as follows. For each catalyst the volumetricreaction constant k_(vol) was calculated using n^(th) order kinetics anda reaction order of 1.0 for HDN and 1.2 for HDS. The relative volumetricactivities (RVA) of the different catalysts of the invention vs acomparative catalyst were subsequently calculated by taking the ratio ofthe reaction constants. In the tables, SA is surface area, PV is porevolume, DMPD is mean pore diameter based on the desorption branch of theN₂ physisorption isotherm, S is sulfur, N is nitrogen, P is pressure,g_(cat) is the amount of catalyst in the reactor, LHSV is liquid hourlyspace velocity and r.o. is reaction order.

Support Preparation

The following supports were made in accordance with the proceduresdescribed below. One support was prepared as a reference (S1, Al₂O₃). Asummary of the properties for each support can be found in Table 1.

Example S1: Comparative S1

Comparative S1 was 100% standard Al₂O₃ prepared via a co-precipitationprocess. Aluminum sulfate (Alum) and sodium aluminate (Natal) were dosedsimultaneously to a heel of water at 60° C. and pH 8.5. The flows ofNatal and Alum were fixed and the pH was controlled constantly with NaOHor H₂SO₄. Total dosing time was approximately 1 hour and the final Al₂O₃concentration in the reactor was approximately 4% on weight basis. ThepH was then raised with NaOH or Natal to approximately 10 and the slurrywas aged for 10 minutes while stirring. The slurry was filtered over afilter cloth and washed with water or a solution of ammoniumbi-carbonate in water until sufficient removal of sodium and sulfate.The cake was dried, extruded and calcined.

Example S2: Support S2

The support S2 was prepared via a co-extrusion process of alumina andtitania filter cakes. The alumina filter cake was prepared via theprocess described in Example S1 (prior extrusion). The titania filtercake was prepared via hydrolysis of an aqueous solution of TiOSO₄ at 99°C. for 5 hours followed by neutralization with NaOH to pH 7. Theprecipitate was filtered and washed salt free using water or ammoniumbi-carbonate solution. The two filter cakes were mixed in a kneader andextruded. The extrudates were calcined at 650° C. for 1 hour underairflow of ca. 10 nL/min. The final composition of the support (drybase) was found to be 49.7 wt. % TiO₂ and 50.3 wt. % Al₂O₃.

Example S3: Support S3

The support S3 was prepared via a co-precipitation process. Aluminumsulfate (Alum) and Titanyl sulfate (TiOSO₄) mixed in one stream andsodium aluminate (Natal) were dosed simultaneously to a heel of water at60° C. and pH 8.5. The flows of Natal and Alum/TiOSO₄ were fixed and thepH was controlled constantly with NaOH or H₂SO₄. Total dosing time wasapproximately 1 hour and the final solid concentration in the reactorwas approximately 4% on weight basis. The pH was then raised with NaOHor Natal to approximately 10 and the slurry was aged for 20 minuteswhile stirring. The slurry was filtered over a filter cloth and washedwith water or a solution of ammonium bi-carbonate in water untilsufficient removal of sodium and sulfate. The cake was dried, extrudedand calcined at 650° C. for 1 hour under airflow of ca. 10 nL/min. Thefinal composition of the support (dry base) was found to be 48.0 wt. %TiO₂ and 52.0 wt. % Al₂O₃.

Example S4: Support S4

The support S4 was prepared by co-precipitation using the same processas was used to prepare support S3, but using different amounts of theTiO₂ and Al₂O₃ precursors. The final composition of the support (drybase) was found to be 20.9 wt. % TiO₂ and 79.1 wt. % Al₂O₃.

Example S5: Support S5

The support S5 was prepared by consecutive precipitation of alumina andtitania. Firstly alumina (boehmite) was precipitated according to theprocedure as described in Example S1 After filtration and properwashing, the precipitate was transferred back to the reactor. Boehmitefilter cake was slurried in a stainless steel vessel with water andstirred while heating up to 60° C. To the slurry TiOSO₄ solution wasdosed at a fixed rate and the pH was controlled at 8.5 via addition ofNaOH solution. The dosing time was 25 minutes at 60° C. The slurry wasthoroughly washed using water or ammonium bi-carbonate solution toremove salts, dried, extruded and calcined at 650° C. for 1 hour underairflow of ca. 10 nL/min. The final composition of the support (drybase) was found to be 21.1 wt. % TiO₂ and 78.9 wt. % Al₂O₃.

Example S6: Support S6

The support S6 was prepared by coating an aqueous titania precursor onalumina extrudates. The extrudates used consisted predominantly ofγ-alumina and had a surface area of 271 m²/g, a pore volume of 0.75 ml/gand a mean pore diameter of 8.7 nm as determined from the N₂physisorption desorption isotherm. The pores of the alumina extrudateswere filled with an aqueous solution of Titanium(IV)bis(ammoniumlactato)dihydroxide, aged for 2 hours at 60° C. and pre-dried in arotating pan and eventually dried overnight at 120° C. The sample wascalcined at 450° C. for 2 hours under airflow. This procedure wasrepeated a second time reaching higher titania loadings. The finalcomposition of the support (dry base) was found to be 27.8 wt. % TiO₂and 72.2 wt. % Al₂O₃.

Example S7: Support S7

The support S7 was prepared by coating an alkoxide titania precursor onalumina extrudates. The extrudates used had the same characteristics asthose used in Example S6. The pores of the alumina were filled withTi-isopropoxide solution in propanol. The aging process was carried outinside an atmosbag filled with a N₂ atmosphere at room temperature for 2hours, and then the same is placed outside of the atmosbag forhydrolysis overnight (at RT). Finally the sample is dried at 120° C.overnight. The sample was calcined at 450° C. for 2 hours. The finalcomposition of the support (dry base) was found to be 18.9 wt. % TiO₂and 81.1 wt. % Al₂O₃.

Example S8: Support S8

The support S8 was prepared by a second coating with an alkoxide titaniaprecursor on the TiO₂—Al₂O₃ extrudates obtained in Example S7. Theprocedure as described in Example S7 was repeated a second time reachinghigher titania loadings. The final composition of the support (dry base)was found to be 43.7 wt. % TiO₂ and 56.3 wt. % Al₂O₃.

Example S9: Comparative S9

The support S9 was prepared by strike-precipitation of alumina andtitania. Natal was diluted in water and under vigorous stirringwaterglass was added while heating at 60° C. To this mixture aluminumsulfate and titanyl sulfate were added in 20 minutes with a final pH of6.5. NaOH was used to adjust the pH to 7.2 and the mixture was aged for1 hour at 60° C. while stirring. The cake is re-slurried with water,brought to pH 10 with ammonia and aged at 95° C. for 1 hour whilestirring. Then, the slurry is filtered and washed with water to removeexcess ammonia, dried, extruded and calcined at 650° C. for 1 hour underairflow of ca. 10 nL/min with 25 vol. % steam. The final composition ofthe support (dry base) was found to be 23.1 wt. % TiO₂, 3.2 wt. % SiO₂and 73.7 wt. % Al₂O₃.

Example S10: Support S10

The support S10 was prepared by strike-precipitation of alumina, titaniaand silica in the same way as S9 using different amounts of the rawmaterials. The final composition of the support (dry base) was found tobe 21.3 wt. % TiO₂, 0.6 wt. % SiO₂ and the rest is Al₂O₃.

Example S11: Comparative S11

The support S11 was prepared by strike-precipitation of alumina, titaniaand silica in the same way as S9 using different amounts of the rawmaterials. In this case, the extrudates were calcined at 750° C. for 1hour under airflow of ca. 10 nL/min with 25 vol. % steam. The finalcomposition of the support (dry base) was found to be 21.0 wt. % TiO₂,9.9 wt. % SiO₂ and the rest is Al₂O₃.

Example S12: Support S12

The support S12 was prepared by strike-precipitation of alumina, titaniaand silica in the same way as S9 using different amounts of the rawmaterials. The final composition of the support (dry base) was found tobe 20.9 wt. % TiO₂, 0.02 wt. % SiO₂ and the rest is Al₂O₃.

Example S13: Support S13

The support S13 was prepared in the same way as S9, but lower TiO₂ andSiO₂ sources were used. The final composition of the support (dry base)was found to be 10.8 TiO₂ wt. %, 0.5 SiO₂ wt. % and 88.7 Al₂O₃ wt. %.

Example S14: Support S14

The support S14 was prepared via a co-precipitation process. Aluminumsulfate (Alum) in one stream and sodium aluminate (Natal) were dosedsimultaneously to a heel of water and waterglass at 50° C. and pH 8.7.The flows of Natal and Alum were fixed and the pH was controlledconstantly with NaOH or H₂SO₄. Total dosing time was approximately 0.5hour and the final solid concentration in the reactor was approximately3.5% on weight basis. The slurry was filtered over a filter cloth andwashed with water. The cake was dried, extruded and calcined at 650° C.with steam (25%) for 1 hour under airflow of ca. 10 nL/min. The finalcomposition of the support (dry base) was found to be 1.0 wt. % SiO₂ andthe rest is Al₂O₃.

Example S15: Support S15

The support S15 was prepared by co-extrusion/kneading of Al₂O₃ cake(S14) and a titanium source. The Titanium(IV)isopropoxide was addedafter 15 minutes kneading time. Later a vent hole was opened in order tolet the alcohol evaporate. The kneaded material was extruded and then,the plate with wet extrudates was placed in the stove and kept thereovernight at 120° C. Finally, the sample was calcined at 710° C. Thefinal composition of the support (dry base) was found to be 10.6 wt. %TiO₂, 0.82 wt. % SiO₂ and the rest is Al₂O₃.

Example S16: Support S16

The support S16 was prepared in the same way as S9, but lower TiO₂ andSiO₂ sources were used. The final composition of the support (dry base)was found to be 5.4 TiO₂ wt. %, 0.57 SiO₂ wt. % and the rest Al₂O₃ wt.%.

Example S17: Support S17

The support S17 was prepared in the same way as S9, but lower TiO₂ andSiO₂ sources were used. The final composition of the support (dry base)was found to be 10.6 TiO₂ wt. %, 0.73 SiO₂ wt. % and the rest Al₂O₃ wt.%.

Example S18: Support S18

The support S18 was prepared in the same way as S9, but lower SiO₂sources were used. The final composition of the support (dry base) wasfound to be 21.6 TiO₂ wt. %, 0.51 SiO₂ wt. % and the rest Al₂O₃ wt. %.

The sodium content present is any of these supports is very low (<0.5 wt%), since it is known as detrimental for the hydroprocessing activity.

TABLE 1 Summary of supports used during examples. Sup- Weight % Weight %SA PV DMPD port Procedure TiO₂ (*) SiO₂ (*) (m²/g) (ml/g) (nm) S1 ref. —— 271 0.84 8.1 S2 co-extrusion 47.9 — 200 0.52 8.7 S3 co-precipitation48.0 — 258 0.64 7.7 S4 co-precipitation 20.9 — 304 0.86 7.9 S5step-precipitation 21.1 — 239 0.78 9.4 S6 coating 27.8 — 275 0.48 7.8 S7coating 18.9 — 271 0.60 8.1 S8 coating 43.7 — 229 0.38 5.5 S9strike-precipitation 23.1 3.2 293 0.56 6.1 S10 strike-precipitation 21.30.6 236 0.59 8.1 S11 strike-precipitation 21.0 9.9 270 0.61 7.1 S12strike-precipitation 20.9 0.02 172 0.40 7.2 S13 strike-precipitation10.8 0.53 240 0.65 9.0 S14 ref. — 1.0 257 0.60 7.2 S15 co-extrusion 10.60.82 225 0.54 7.4 S16 strike-precipitation 5.4 0.57 216 0.63 9.0 S17strike-precipitation 10.6 0.73 225 065 9.0 S18 strike-precipitation 21.60.51 219 0.59 8.5 * based on the total weight of the support dry baseCatalyst Preparation and Testing

Example A: Positive Effect of TiO₂ Addition in Different Amounts and ViaDifferent Preparation Methods on the Activity of NiMo Catalysts

The following examples illustrate the positive effect of TiO₂ additionin the support on the activity of NiMo catalysts when combined withorganics in the catalyst preparation. The catalysts were prepared asdescribed in examples A1-A11 using the same method to apply metals andorganic additives to the catalysts and have a comparable volume loadingof metals in the reactor. Approximately 0.9 ml of each of the catalystswas tested in a multi-reactor unit under medium pressure ultra-lowsulfur diesel conditions. Table 2 shows the pre-sulfidation and testconditions and Table 3 shows the activity results.

TABLE 2 Pre-sulfiding and test (medium P ULSD) format used for activitytesting of NiMo examples A. Pre-sulfiding conditions LHSV P H₂/oilTemperature Time Feed (1/hr) (bar) (Nl/l) (° C.) (hours) Spiked LGO 3 45300 320 24 Testing conditions P H₂/oil Temperature Time @ Feed (bar)(Nl/l) (° C.) condition (days) SRGO 1.09 wt. % S 45 300 350 4 and 200ppmN

Example A1: Comparative A1

Comparative A1 was prepared by consecutive impregnation of supportComparative A1 with (i) a NiMoP aqueous solution and, after drying, (ii)with thioglycolic acid. The metal loaded intermediate was prepared fromsupport S1 using impregnation with an amount of aqueous NiMoP solutionequivalent to fill 105% of the pore volume, as is known for a personskilled in the art. The pore volume of the support was determined by aso-called water PV measurement in which the point of incipient wetnesswas determined by addition of water to the carrier extrudates. The NiMoPsolution was prepared by dispersing of the required amount of NiCO₃ inwater. The solution was then heated to 60° C. while stirring. Half ofthe required H₃PO₄ was added carefully to the solution and subsequentlyMoO3 was added in small portions. The solution was heated up to 92° C.to obtain a clear solution. Finally, the rest of the H₃PO₄ was added tothe solution and water was added to reach the concentration required forthe desired metal loading. After impregnation, the extrudates wereallowed to age for 1 hour in a closed vessel, after which drying wascarried out at 120° C. for at least one hour. Subsequently, impregnationof the thus formed metal loaded intermediate with thioglycolic acid wascarried out with neat thioglycolic acid to reach a loading of thiscompound on the catalysts of 3.5 mol/mol metals (Mo+Ni) in the catalystat ambient temperature. The thus formed composite was further aged for 2hour, while rotating. The extrudates were then poured out into a petridish and placed in a static oven at 80° C. for 16 hours. Bothimpregnations were performed in a rotating pan. The composition of themetal impregnated dried catalyst (dry base) was 23.0 wt. % MoO₃, 4.5 wt.% NiO, 4.0 wt. % P₂O₅ and the rest is Al₂O₃.

Example A2: Invention A2

Invention A2 was prepared using support S2 and the same preparationprocess as A1. The composition of the metal impregnated dried catalyst(dry base) was 17.2 wt. % MoO₃ and 3.3 wt. % NiO, 3.1 wt. % P₂O₅, 38.6wt. % TiO₂ and the rest is Al₂O₃.

Example A3: Invention A3

Invention A3 was prepared using support S3 and the same preparationprocess as A1. The composition of the metal impregnated dried catalyst(dry base) was 19.4 wt. % MoO₃ and 3.8 wt. % NiO, 3.5 wt. % P₂O₅, 37.4wt. % TiO₂ and the rest is Al₂O₃.

Example A4: Invention A4

Invention A4 was prepared using support S4 and the same preparationprocess as A1. The composition of the metal impregnated dried catalyst(dry base) was 23.7 wt. % MoO₃ and 4.5 wt. % NiO, 4.1 wt. % P₂O₅, 13.0wt. % TiO₂ and the rest is Al₂O₃.

Example A5: Invention A5

Invention A5 was prepared using support S5 and the same preparationprocess as A1. The composition of the metal impregnated dried catalyst(dry base) was 24.4 wt. % MoO₃ and 4.7 wt. % NiO, 4.3 wt. % P₂O₅, 13.5wt. % TiO₂ and the rest is Al₂O₃.

Example A6: Invention A6

Invention A6 was prepared using support S6 and the same preparationprocess as A1. The composition of the metal impregnated dried catalyst(dry base) was 18.0 wt. % MoO₃ and 3.4 wt. % NiO, 3.1 wt. % P₂O₅, 21.2wt. % TiO₂ and the rest is Al₂O₃.

Example A7: Invention A7

Invention A7 was prepared using support S7 and the same preparationprocess as A1. The composition of the metal impregnated dried catalyst(dry base) was 20.1 wt. % MoO₃ and 4.0 wt. % NiO, 3.5 wt. % P₂O₅, 12.6wt. % TiO₂ and the rest is Al₂O₃.

Example A8: Invention A8

Invention A8 was prepared using support S8 and the same preparationprocess as A1. The composition of the metal impregnated dried catalyst(dry base) was 18.7 wt. % MoO₃ and 3.7 wt. % NiO, 3.4 wt. % P₂O₅, 25.9wt. % TiO₂ and the rest is Al₂O₃.

Example A9: Comparative A9

Comparative A9 was prepared using support S1 and the same preparationprocess as A1. The composition of the metal impregnated dried catalyst(dry base) was 24.8 wt. % MoO₃ and 4.4 wt. % NiO, 4.3 wt. % P₂O₅ and therest is Al₂O₃.

Example A10: Invention A10

Invention A10 was prepared using support S10 and the same preparationprocess as A1. The composition of the metal impregnated dried catalyst(dry base) was 22.0 wt. % MoO₃ and 3.7 wt. % NiO, 3.8 wt. % P₂O₅, 0.37wt. % SiO₂, 15.0 TiO₂ wt. % and the rest is Al₂O₃.

Example A11: Invention A11

Invention A11 was prepared using support S13 and the same preparationprocess as A1. The composition of the metal impregnated dried catalyst(dry base) was 23.6 wt. % MoO₃ and 4.1 wt. % NiO, 4.0 wt. % P₂O₅, 0.36wt. % SiO₂, 7.4 wt. % TiO₂ and the rest is Al₂O₃.

TABLE 3 The effect of the addition of TiO₂ in combination with anorganic on the activity of supported NiMo catalysts in medium P ULSDactivity testing. RVA RVA g_(CAT) db mg MoO₃ LHSV N HDN LHSV S HDSExample Support Reactor Reactor HDN (ppm) r.o. 1.0 HDS (ppm) r.o. 1.2Comparative A1 S1 0.720 184 4.0 49 100% 2.5 151 100% Invention A2 S20.881 168 40 108% 99 113% Invention A3 S3 0.794 171 22 152% 42 151%Invention A4 S4 0.647 170 44 105% 119 107% Invention A5 S5 0.640 173 35123% 65 130% Invention A6 S6 0.990 189 9 211% 24 170% Invention A7 S70.844 184 19 165% 33 169% Invention A8 S8 0.936 195 11 197% 28 171%Comparative A9 S1 0.719 198 58 100% 2.7 144 100% Invention A10 S10 0.855209 9 246% 24 177% Invention A11 S13 0.820 215 19 190% 29 169%

As can be seen in Table 3, the catalysts that were prepared using aTi-containing support are significantly more active in HDN and HDS thanthe comparative catalyst without any Ti (A1, A10) using the sameS-containing organic additive and impregnation method. Since differentLHSV have been used, RVAs of Inventions A2-A9 are relative to theactivity of Comparative A1 and RVAs of Inventions A11-A12 are relativeto Comparative A10.

The prior art teaches that it is critical to obtain a good dispersion ofthe TiO₂ phase in TiO₂/Al₂O₃ based hydroprocessing catalysts enable toobserve the most positive effect of TiO₂ addition on catalyst activity.This is for example expressed in [U.S. Pat. No. 9,061,265B2] in a claimregarding the relative intensity of the anatase and rutile TiO₂ peaksvs. the intensity of the γ-Al₂O₃ peak at ° 2 theta in the XRD pattern.In FIG. 1, the XRD patterns of the catalysts of the invention arepresented. It can be observed that the intensity of the anatase TiO₂(101) peak (around 26° 2 theta) vs the γ-Al₂O₃ (400) peak (around 46° 2theta) ratio varies greatly between the different catalysts of theinvention, with a number of catalysts exhibiting a anatase/γ-Al₂O₃ peakratio that is much higher than what is claimed to be advantageous in theprior art. Also, there seems to be no obvious link between TiO₂dispersion and catalyst activity, when applying the preparation methodof the invention. For example, Invention A5 shows a relative anataseTiO₂ peak vs γ-Al₂O₃ peak intensity that is much higher than what isobserved for Invention A4, which is likewise prepared via precipitationand roughly contains the same wt. % of TiO₂. To our surprise, and incontrast to what is taught in the art, the activity of Invention A5 issignificantly higher than that of Invention A4. Apparently thepreparation method used and the organics applied removes the need for avery good TiO₂ dispersion in preparation of a highly active TiO₂/Al₂O₃based hydroprocessing catalyst.

Examples B: Positive Effect of TiO₂ Addition in Different Amounts andVia Different Preparation Methods on the Activity of CoMo Catalysts

These examples illustrate the positive effect of addition of TiO₂ in thesupport on the activity of CoMo catalysts when combined with organics inthe preparation in a wide range of TiO₂ contents. Catalysts B1-B8 wereall prepared using the same method to apply metals and thioglycolic acidto the catalyst and have a comparable volume loading of metals in thereactor. The catalysts were tested in a multi-reactor unit under mediumpressure ultra-low sulfur diesel conditions. Table 4 shows thepre-sulfidation and Table 5 shows the activity results.

TABLE 4 Pre-sulfiding and test (medium P ULSD) format used for activitytesting of CoMo examples B. Pre-sulfiding conditions LHSV P H₂/oilTemperature Time Feed (1/hr) (bar) (Nl/l) (° C.) (hours) Spiked LGO 3 45300 320 24 Testing conditions P H₂/oil Temperature Time @ Feed (bar)(Nl/l) (° C.) condition (days) SRGO with 1.09 wt. % 45 300 350 4 S and200 ppmN

Example B1: Comparative B1

Comparative B1 was prepared by consecutive impregnation of supportComparative A1 with (i) a CoMoP aqueous solution and, after drying, (ii)with thioglycolic acid. Both impregnations were performed in a rotatingpan. The metal loaded intermediate was prepared from support S1 usingimpregnation with an amount of aqueous CoMoP solution equivalent to fill105% of the pore volume, as is known for a person skilled in the art.The pore volume of the support was determined by a so-called water PVmeasurement in which the point of incipient wetness was determined byaddition of water to the carrier extrudates. The CoMoP solution wasprepared by dispersing of the required amount of CoCO₃ in water. Thesolution was then heated to 60° C. while stirring. Half of the requiredH₃PO₄ was added carefully to the solution and subsequently MoO₃ wasadded in small portions. The solution was heated up to 92° C. to obtaina clear solution. Finally, the rest of the H₃PO₄ was added to thesolution and water was added to reach the concentration required for thedesired metal loading. After impregnation, the extrudates were allowedto age for 1 hour in a closed vessel, after which drying was carried outat 120° C. for at least one hour. Subsequently, impregnation of the thusformed metal loaded intermediate with thioglycolic acid was carried outwith neat thioglycolic acid to reach a loading of this compound on thecatalysts of 3.5 mol/mol metals (Mo+Co) in the catalyst. The thus formedcomposite was further aged for 2 hour, while rotating. The extrudateswere then poured out into a petri dish and placed in a static oven at80° C. for 16 hours. The composition of the metal impregnated driedcatalyst (dry base) was 24.0 wt. % MoO₃ and 4.6 wt. % CoO, 4.2 wt. %P₂O₅ and the rest is Al₂O₃.

Example B2: Invention B2

Invention B2 was prepared using support S3 and the same preparationprocess as B1. The composition of the metal impregnated dried catalyst(dry base) was 19.1 wt. % MoO₃ and 3.6 wt. % CoO, 3.3 wt. % P₂O₅, 37.2wt. % TiO₂ and the rest is Al₂O₃.

Example B3: Invention B3

Invention B3 was prepared using support S5 and the same preparationprocess as B1. The composition of the metal impregnated dried catalyst(dry base) was 19.8 wt. % MoO₃ and 3.8 wt. % CoO, 3.3 wt. % P₂O₅, 12.4wt. % TiO₂ and the rest is Al₂O₃.

Example B4: Inventive B4

Invention B4 was prepared using support S6 and the same preparationprocess as B1. The composition of the metal impregnated dried catalyst(dry base) was 19.1 wt. % MoO₃ and 3.6 wt. % CoO, 3.3 wt. % P₂O₅, 20.7wt. % TiO₂ and the rest is Al₂O₃.

Example B5: Invention B5

Invention B5 was prepared using support S7 and the same preparationprocess as B1. The composition of the metal impregnated dried catalyst(dry base) was 19.8 wt. % MoO₃ and 3.8 wt. % CoO, 3.5 wt. % P₂O₅, 20.1wt. % TiO₂ and the rest is Al₂O₃.

Example B6: Comparative B6

Comparative B6 was prepared using support S1 and the same preparationprocess as B1. The composition of the metal impregnated dried catalyst(dry base) was 26.1 wt. % MoO₃ and 4.8 wt. % CoO, 4.4 wt. % P₂O₅ and therest is Al₂O₃.

Example B7: Invention B7

Invention B7 was prepared using support S10 and the same preparationprocess as B1. The composition of the metal impregnated dried catalyst(dry base) was 23.4 wt. % MoO₃ and 3.9 wt. % CoO, 4.0 wt. % P₂O₅, 0.36wt. % SiO₂, 14.7 wt. % TiO₂ and the rest is Al₂O₃.

Example B8: Invention B8

Invention B8 was prepared using support S13 and the same preparationprocess as B1. The composition of the metal impregnated dried catalyst(dry base) was 20.5 wt. % MoO₃ and 4.3 wt. % CoO, 4.3 wt. % P₂O₅, 0.36wt %. SiO₂, 7.2 wt. % TiO₂ and the rest is Al₂O₃.

TABLE 5 The effect of the addition of a sulfur containing organic incombination with TiO₂-containing support in the activity of CoMocatalysts in medium P ULSD activity testing. mg RVA g_(CAT) db MoO₃ LHSVN HDN Example Support Reactor Reactor HDN (ppm) r.o. 1 Comparative B1 S10.730 194 3.5 50 100% Invention B2 S3 0.837 180 26 158% Invention B3 S50.829 182 34 131% Invention B4 S6 0.919 187 21 160% Invention B5 S70.891 196 20 174% Comparative B6 S1 0.701 203 4.0 88 100% Invention B7S10 0.893 232 19 259% Invention B8 S13 0.812 226 40 186%

As can be seen in Table 5, the catalysts that were prepared on aTi-containing supports (B2-B5, B7 and B8) are significantly more activein HDN than the comparative catalysts without any Ti (B1 and B6) usingthe same organic additive and impregnation method. Since different LHSVhave been used, RVAs of Inventions B2-B5 are relative to the activity ofComparative B1 and RVA of Inventions B7 and B8 are relative toComparative B6.

Examples C: The Effect of Organics Addition on Activity and the LimitedEffect of SiO₂-Content on Activity of TiO₂—Al₂O₃ Supported CoMoCatalysts

In the following examples it is illustrated that the inclusion of SiO₂in the catalyst composition has only a very modest, if any effect oncatalyst activity. Supports with a variation in SiO₂ content wereprepared using a co-precipitation method and these were used to makeCoMo catalysts according to the preparation method of the invention andcomparable metal loadings per reactor volume. The catalysts were testedin a multi-reactor unit under medium pressure hydrotreating of a SRGO.Table 6 shows the pre-sulfidation and test conditions that were used fortesting and Tables 7 shows the activity results that were obtained.

TABLE 6 Pre-sulfiding and test (medium P ULSD) format used for activitytesting of CoMo examples C. Pre-sulfiding conditions LHSV P H₂/oilTemperature Time Feed (1/hr) (bar) (Nl/l) (° C.) (hours) Spiked LGO 3 45300 320 24 Testing conditions P H₂/oil Temperature Time @ Feed (bar)(Nl/l) (° C.) condition (days) SRGO with 1.4 wt. % 45 300 350 3 S and200 ppmN

Example C1: Comparative C1

Comparative C1 was prepared using support S1 and impregnated with CoMoPaqueous solution without organics. Preparation of the CoMoP solution andimpregantion was done according to the procedure described in ExampleB1. The composition of the metal impregnated dried catalyst (dry base)was 26.4 wt. % MoO₃ and 4.8 wt. % CoO, 4.2 wt. % P₂O₅ and the rest isAl₂O₃.

Example C2: Comparative C2

Comparative C2 was prepared using support S9 and impregnated, as C1,with a CoMoP aqueous solution without organics. The composition of themetal impregnated dried catalyst (dry base) was 24.1 wt. % MoO₃ and 3.6wt. % CoO, 3.9 wt. % P₂O₅, 15.3 wt. % TiO₂.

Example C3: Comparative C3

Comparative C3 was prepared using support S9. Firstly, it wasimpregnated with CoMoP aqueous solution as Example C1 and after drying asecond impregnation with thioglycolic acid (3.5 mol/mol metals in thecatalyst) in a rotating pan was performed. The intermediate was furtheraged for 2 hours, while rotating, and then poured out into a petri dishand placed in a static oven at 80° C. for 16 hours. The composition ofthe metal impregnated dried catalyst (dry base) was 24.2 wt. % MoO₃ and4.5 wt. % CoO, 4.1 wt. % P₂O₅, 13.9 wt. % TiO₂, 1.8 wt. % SiO₂ wt % andthe rest is Al₂O₃.

Example C4: Comparative C4

Invention C5 was prepared using support S10 and the same impregnationprocedure as Example C3. The composition of the metal impregnated driedcatalyst (dry base) was 26.1 wt. % MoO₃ and 4.8 wt. % CoO, 4.3 wt. %P₂O₅, 13.5 wt. % TiO₂, 6.4 wt. % SiO₂ and the rest is Al₂O₃.

Example C5: Invention C5

Invention C4 was prepared using support S11 and the same impregnationprocedure as Example C3. The composition of the metal impregnated driedcatalyst (dry base) was 22.3 wt. % MoO₃ and 4.3 wt. % CoO, 3.8 wt. %P₂O₅, 14.5 wt. % TiO₂, 0.4 wt. % SiO₂ and the rest is Al₂O₃.

Example C6: Invention C6

Invention C6 was prepared using support S12 and the same impregnationprocedure as in Example C3. The composition of the metal impregnateddried catalyst (dry base) was 24.4 wt. % MoO₃ and 4.5 wt. % CoO, 4.1 wt.% P₂O₅, 13.7 wt. % TiO₂, 0.1 wt. % SiO₂ and the rest is Al₂O₃.

TABLE 7 The effect of the addition of an organic in combination withTiO₂-containing support in the activity of CoMo catalysts in medium PULSD activity testing and the limited effect of SiO₂ addition. RVA mgRVA HDS SiO₂ g_(CAT) db MoO₃ LHSV N HDN LHSV S r.o. Example Support wt.% Additive Reactor Reactor HDN (ppm) r.o. 1 HDS (ppm) 1.2 Comparative C1S1 — No organic 0.732 211 3.7 86 100% 2.6 211 100% Comparative C2 S9 3.2No organic 0.778 220 56 145% 150 111% Comparative C3 S9 3.2 Thioglycolicacid 0.798 222 7 345% 23 186% Comparative C4 S11 9.9 Thioglycolic acid0.703 219 16 271% 38 165% Invention C5 S10 0.6 Thioglycolic acid 0.774218 10 319% 26 182% Invention C6 S12 — Thioglycolic acid 0.912 216 19258% 35 171%

From the test results in Table 7, it can be observed that regardless ofthe SiO₂ in the support, a large activity benefit is observed for thecatalysts based on a TiO₂/Al₂O₃ support in combination with thepreparation method that involves the use of organics. The effect of theorganic additive on activity (delta C3 vs C2) is much larger than theeffect of the SiO₂ content (differences between C3, C4, C5 and C6).Apparently, the preparation method based on the use of organic additivesremoves the need of SiO₂ addition for the preparation of efficientTiO₂/Al₂O₃ based hydroprocessing catalysts.

It can be concluded that, in contrast to what is described in the priorart, using the preparation method disclosed in which organics are usedin the preparation, the dispersion of the TiO₂ phase within theTiO₂/Al₂O₃ support does not have an obvious effect on catalyst activity.Likewise, the addition of SiO₂ to the catalyst composition does notresult in a higher activity. Hence, the preparation method based on theuse of organic additives as disclosed offers the advantage that allowsgreater flexibility in the design of a manufacturing process. Forexample, co-extrusion of Ti-precursors could be used, which would removethe need for cumbersome washing steps that are required when Ti is addedduring precipitation. Also a higher calcination temperature could beapplied to obtain a certain required pore diameter without a negativeeffect of this procedure resulting in a decrease of the TiO₂ dispersion.

Examples D: The Effect of a Wide Variation of Organics Additives on theActivity of TiO₂/Al₂O₃Supported NiMo and CoMo Catalysts

In the following examples it is illustrated that the use of differentorganic additives has a positive effect on the catalyst activity. Afixed TiO₂/Al₂O₃ support with a variation in the organic additive andcomparable metal loading catalysts were prepared. The catalysts weretested in a multi-reactor unit under medium pressure hydrotreating of aSRGO. Table 8 shows the pre-sulfidation and test conditions that wereused for testing and Tables 9 (NiMo) and 10 (CoMo) shows the activityresults that were obtained.

TABLE 8 Pre-sulfiding and test (medium P ULSD) format used for activitytesting of NiMo and CoMo catalysts from examples D. Pre-sulfidingconditions LHSV P H₂/oil Temperature Time Feed (1/hr) (bar) (Nl/l) (°C.) (hours) Spiked LGO 3 45 300 320 24 Testing conditions P H₂/oilTemperature Time @ Feed (bar) (Nl/l) (° C.) condition (days) SRGO with1.09 wt. % 45 300 350 4 S and 200 ppmN

Example D1: Comparative D1

Comparative D1 was prepared using support Sand impregnated with NiMoPaqueous solution without organics. An amount of aqueous NiMoP solutionequivalent to fill 105% of the pore volume was used for impregnation, asis known for a person skilled in the art. The pore volume of the supportwas determined by a so-called water PV measurement in which the point ofincipient wetness was determined by addition of water to the carrierextrudates. The NiMoP solution was prepared by dispersing of therequired amount of NiCO₃ in water. The solution was then heated to 60°C. while stirring. Half of the required H₃PO₄ was added carefully to thesolution and subsequently MoO₃ was added in small portions. The solutionwas heated up to 92° C. to obtain a clear solution. Finally, the rest ofthe H₃PO₄ was added to the solution and water was added to reach theconcentration required for the desired metal loading. Afterimpregnation, the extrudates were allowed to age for 1 hour in a closedvessel, after which drying was carried out at 120° C. for at least onehour. The composition of the metal impregnated dried catalyst (dry base)was 22.1 wt. % MoO₃ and 3.6 wt. % NiO, 3.8 wt. % P₂O₅, 0.38 wt. % SiO₂,15.0 wt. % TiO₂ and the rest is Al₂O₃.

Example D2: Invention D2

Invention D2 was prepared using Comparative D1 and a subsequentimpregnation with Glyoxilic acid to reach 15 wt. % in the finalcatalyst. The composition of the metal impregnated dried catalyst (drybase) was as D1.

Example D3: Invention D3

Invention D3 was prepared using Comparative D1 and a subsequentimpregnation with Resorcinol to reach 15 wt. % in the final catalyst.The composition of the metal impregnated dried catalyst (dry base) wasas D1.

Example D4: Invention D4

Invention D4 was prepared using Comparative D1 and a subsequentimpregnation with Triethylene glycol to reach 15 wt. % in the finalcatalyst. The composition of the metal impregnated dried catalyst (drybase) was as D1.

Example D5: Comparative D5

Comparative D5 was prepared in the same way as Comparative D1. Thecomposition of the metal impregnated dried catalyst (dry base) was 23.6wt. % MoO₃ and 4.1 wt. % NiO, 4.1 wt. % P₂O₅, 0.39 wt. % SiO₂, 14.4 wt.% TiO₂ and the rest is Al₂O₃.

Example D6: Invention D6

Invention D6 was prepared using Comparative D5 and a subsequentimpregnation with Itaconic acid to reach 15 wt. % in the final catalyst.The composition of the metal impregnated dried catalyst (dry base) wasas D5.

Example D7: Invention D7

Invention D6 was prepared using Comparative D5 and a subsequentimpregnation with Diethylene Glycol Butyl Ether to reach 15 wt. % in thefinal catalyst. The composition of the metal impregnated dried catalyst(dry base) was as D5.

Example D8: Invention D8

Invention D8 was prepared using Comparative D5 and a subsequentimpregnation with Glucose to reach 15 wt. % in the final catalyst. Thecomposition of the metal impregnated dried catalyst (dry base) was asD5.

Example D9: Invention D9

Invention D9 was prepared using Comparative D5 and a subsequentimpregnation with Ribose to reach 15 wt. % in the final catalyst. Thecomposition of the metal impregnated dried catalyst (dry base) was asD5.

TABLE 9 The effect of the addition of an organic in combination withTiO₂-containing support in the activity of NiMo catalysts in medium PULSD activity testing. mg RWA RWA g_(CAT) db MoO₃ LHSV N HDN LHSV S HDSExample Support Additive Reactor Reactor HDN (ppm) r.o. 1 HDS (ppm) r.o.1.2 Comparative D1 S10 No organic 0.841 207 4.0 46 100% 2.7 61 100%Invention D2 Glyoxilic acid 0.857 211 27 129% 26 125% Invention D3Resorcinol 0.830 204 22 149% 27 130% Invention D4 Triethylene glycol0.847 208 19 150% 50 104% Invention D6 Itaconic acid 0.886 233 14 161%3.0 44 133% Invention D7 DiethyleneGlycol 0.873 219 11 178% 28 156%Butyl Ether Invention D8 Glucose 0.907 238 2 257% 21 158% Invention D9Ribose 0.918 230 3 256% 21 165%

As can be observed in Table 9, there is a difference in catalyst intake,and MoO₃ loading in the reactor between the set of catalysts D1-D4(based in D1) and D6-D9 (based on D5). To be able to compare theactivity of the different catalysts, it was decided to determinecatalyst activities on a wt-basis and compare the relative weight basedactivity (RWA) of all catalysts to Comparative D1. It becomes quiteclear that the addition of a wide variety of different organic additivesto NiMo catalysts based on a TiO₂—Al₂O₃(S10) support increasessignificantly the HDN and HDS activity of these catalysts.

Example D10: Comparative D10

Comparative D10 was prepared using support S10 and impregnated withCoMoP aqueous solution without organics. The CoMoP solution was preparedby dispersing of the required amount of CoCO₃ in water. The solution wasthen heated to 60° C. while stirring. Half of the required H₃PO₄ wasadded carefully to the solution and subsequently MoO₃ was added in smallportions. The solution was heated up to 92° C. to obtain a clearsolution. Finally, the rest of the H₃PO₄ was added to the solution andwater was added to reach the concentration required for the desiredmetal loading. After impregnation, the extrudates were allowed to agefor 1 hour in a closed vessel, after which drying was carried out at120° C. for at least one hour. The composition of the metal impregnateddried catalyst (dry base) was 22.2 wt. % MoO₃ and 3.8 wt. % CoO, 3.9 wt.% P₂O₅, 0.37 wt. % SiO₂, 15.0 wt. % TiO₂ and the rest is Al₂O₃.

Example D11: Invention D11

Invention D11 was prepared using Comparative D10 and a subsequentimpregnation with Glucose to reach 15 wt. % in the final catalyst. Thecomposition of the metal impregnated dried catalyst (dry base) was asD10.

Example D12: Invention D12

Invention D12 was prepared using Comparative D10 and a subsequentimpregnation with 3-hydroxybutyric acid to reach 15 wt. % in the finalcatalyst. The composition of the metal impregnated dried catalyst (drybase) was as D10.

Example D13: Invention D13

Invention D13 was prepared using Comparative D10 and a subsequentimpregnation with Ribose to reach 15 wt. % in the final catalyst. Thecomposition of the metal impregnated dried catalyst (dry base) was asD10.

Example D14: Invention D14

Invention D14 was prepared using Comparative D10 and a subsequentimpregnation with Triethylene glycol to reach 15 wt. % in the finalcatalyst. The composition of the metal impregnated dried catalyst (drybase) was as D10.

Example D15: Invention D15

Invention D15 was prepared using Comparative D10 and a subsequentimpregnation with 1,2-propanediol to reach 15 wt. % in the finalcatalyst. The composition of the metal impregnated dried catalyst (drybase) was as D10.

TABLE 10 The effect of the addition of an organic in combination withTiO₂-containing support in the activity of CoMo catalysts in medium PULSD activity testing. mg RVA RVA g_(CAT) db MoO₃ LHSV N HDN LHSV S HDSExample Support Additive Reactor Reactor HDN (ppm) r.o. 1 HDS (ppm) r.o.1.2 Comparative D10 S10 No organic 0.845 209 4.0 66 100% 2.7 105 100%Invention D11 Glucose 0.848 209 46 129% 48 128% Invention D123-hydroxybutyric 0.842 208 50 129% 54 127% acid Invention D13 Ribose0.847 209 49 128% 57 124% Invention D14 Triethylene glycol 0.853 211 53116% 54 122% Invention D15 1,2-propanediol 0.853 211 56 113% 66 116%

As observed in Table 10, the addition of an organic additive (widevariation) on CoMo catalysts based on a TiO₂—Al₂O₃(S10) supportincreases significantly the HDN and HDS activity of these catalysts.Activity of all catalysts has been related to Comparative Don a relativevolumetric activity (RVA) basis, as in this case all catalysts werebased on the same intermediate catalyst (D10) and catalyst intake andMoO₃ loading per reactor were almost identical for all catalysts.

Examples E: Synergistic Effect of the Use of Organics Additives inCombination with Ti—Al₂O₃ Supports on the Activity of NiMo Catalysts

In the following examples, it is illustrated that the use of aTiO₂/Al₂O₃ support in combination with organic additives results in asynergetic effect. The activity benefit of applying a TiO₂/Al₂O₃ supportin combination with organics is higher than can be expected based on theseparate contributions of the (i) TiO₂/Al₂O₃ support and (ii) theorganics as determined in separate experiments and can therefore beregarded as surprising. The catalysts presented are NiMo grades withcomparable metal loadings and are based on the same TiO₂—Al₂O₃ supportand the Al₂O₃ counterpart. The catalysts were tested in a multi-reactorunit under medium pressure ultra-low sulfur diesel conditions. Table 11shows the experimental settings for the pre-sulfidation and testconditions and Tables 12, 13 and 14 shows the amount of catalyst thatwas loaded in the different reactors and the activity results.

TABLE 11 Pre-sulfiding and test (medium P ULSD) format used for activitytesting of NiMo catalysts from example E. Pre-sulfiding conditions LHSVP H₂/oil Temperature Time Feed (1/hr) (bar) (Nl/l) (° C.) (hours) SpikedLGO 3 45 300 320 24 Testing conditions P H₂/oil Temperature Time @ Feed(bar) (Nl/l) (° C.) condition (days) SRGO with 1.09 wt. % 45 300 350 4 Sand 200 ppmN

Example E1: Comparative E1

Comparative E1 was prepared using support S1 and impregnated with NiMoPaqueous solution without organics. An amount of aqueous NiMoP solutionequivalent to fill 105% of the pore volume was used for impregnation, asis known for a person skilled in the art. The pore volume of the supportwas determined by a so-called water PV measurement in which the point ofincipient wetness was determined by addition of water to the carrierextrudates. The NiMoP solution was prepared by dispersing of therequired amount of NiCO₃ in water. The solution was then heated to 60°C. while stirring. Half of the required H₃PO₄ was added carefully to thesolution and subsequently MoO₃ was added in small portions. The solutionwas heated up to 92° C. to obtain a clear solution. Finally, the rest ofthe H₃PO₄ was added to the solution and water was added to reach theconcentration required for the desired metal loading. Afterimpregnation, the extrudates were allowed to age for 1 hour in a closedvessel, after which drying was carried out at 120° C. for at least onehour. The composition of the metal impregnated dried catalyst (dry base)was 23.8 wt. % MoO₃ and 4.5 wt. % NiO, 4.1 wt. % P₂O₅ and the rest isAl₂O₃.

Example E2: Comparative E2

Comparative E2 was prepared using S10 and the same impregnation methodas E1. The composition of the metal impregnated dried catalyst (drybase) was 21.3 wt. % MoO₃ and 4.0 wt. % NiO, 3.6 wt. % P₂O₅, 0.48 wt. %SiO₂, 15.3 wt. % TiO₂ and the rest is Al₂O₃.

Example E3: Comparative E3

Comparative E3 was prepared using S1 and the same impregnation procedureas E1, but with the addition of Gluconic acid with 0.42 mol/mol Mo inthe metal impregnation solution. The composition of the metalimpregnated dried catalyst (dry base) based on theoretical loading was24.1 wt. % MoO₃ and 4.0 wt. % NiO, 4.0 wt. % P₂O₅ and the rest is Al₂O₃.

Example E4: Invention E4

Invention E4 was prepared using S10 and impregnated as E3. Thecomposition of the metal impregnated dried catalyst (dry base) based ontheoretical loading was 21.0 wt. % MoO₃ and 3.5 wt. % NiO, 3.5 wt. %P₂O₅, 0.42 wt. % SiO₂, 15.3 wt. % TiO₂ and the rest is Al₂O₃.

TABLE 12 The effect of the addition of gluconic acid in combination withTiO₂-containing support in the activity of NiMo catalysts in medium PULSD activity testing. mg RVA RVA g_(CAT) db MoO₃ LHSV N HDN LHSV S HDSExample Support Additive Reactor Reactor HDN (ppm) r.o. 1 HDS (ppm) r.o.1.2 Comparative E1 S1 No organic 0.746 200 4.0 76 100% 3.0 280 100%Comparative E2 S10 No organic 0.876 204 41 154% 120 134% Comparative E3S1 Gluconic Acid 0.744 199 61 131% 224 117% Invention E4 S10 GluconicAcid 0.880 205 15 241% 47 179% S_(xy) 56 28

As can be observed in Table 12, the activity of catalyst of theInvention E4 is larger than could be expected based on the addedbenefits of Ti-containing support (E2 without gluconic acid) and the useof gluconic acid as organic additive (E3 without Ti-support). To oursurprise, the combination of a Ti-containing support and the use ofgluconic acid as organic additive (Invention E4) show greater activityimprovement than individual effects of support (E2) or organic (E3)relative to Comparative E1.

To determine the extent of the synergy between the effect of (i) TiO₂addition to the support and (ii) addition of S-containing organics oncatalyst activity, we determined Synergy factor Sxy as defined inEquation 1. RVA_(0,0) is the relative activity of the reference catalyst(without Ti (x) or organics (y)) Values for ax and by were determinedfrom the RVA of the comparative catalyst that is based on the Al₂O₃support with the same organics (RVA_(x,0)=RVA_(0,0)+ax) and the RVA ofthe comparative catalyst based on the TiO₂—Al₂O₃ support withoutorganics (RVA_(0,y)=RVA_(0,0)+by). A positive value of Sxy signifiesthat the activity of catalysts of the invention is higher than could beexpected based on the individual contributions of the support and theorganics on catalyst activity.RVA _(x,y) =RVA _(0,0) +ax+by+Sxy  [Eq. 1]

Example E5: Comparative E5

Comparative E5 was prepared using support S1 and impregnated with NiMoPaqueous solution without organics. An amount of aqueous NiMoP solutionequivalent to fill 105% of the pore volume was used for impregnation, asis known for a person skilled in the art. The pore volume of the supportwas determined by a so-called water PV measurement in which the point ofincipient wetness was determined by addition of water to the carrierextrudates. The NiMoP solution was prepared by dispersing of therequired amount of NiCO₃ in water. The solution was then heated to 60°C. while stirring. Half of the required H₃PO₄ was added carefully to thesolution and subsequently MoO₃ was added in small portions. The solutionwas heated up to 92° C. to obtain a clear solution. Finally, the rest ofthe H₃PO₄ was added to the solution and water was added to reach theconcentration required for the desired metal loading. Afterimpregnation, the extrudates were allowed to age for 1 hour in a closedvessel, after which drying was carried out at 120° C. for at least onehour. The composition of the metal impregnated dried catalyst (dry base)was 24.8 wt. % MoO₃ and 4.4 wt. % NiO, 4.3 wt. % P₂O₅ and the rest isAl₂O₃.

Example E6: Comparative E6

Comparative E6 was prepared using S10 and the same impregnation methodas E5. The composition of the metal impregnated dried catalyst (drybase) was 22.0 wt. % MoO₃ and 3.8 wt. % NiO, 3.8 wt. % P₂O₅, 0.37 wt. %SiO₂, 15.0 wt. % TiO₂ and the rest is Al₂O₃.

Example E7: Comparative E7

Comparative E7 was prepared using S1 and impregnated as E5. Then asubsequent impregnation was performed with 1,2-propanediol to reach 15wt. % in the final catalyst. The composition of the metal impregnateddried catalyst (dry base) was 25.9 wt. % MoO₃ and 4.3 wt. % NiO, 4.4 wt.% P₂O₅ and the rest is Al₂O₃.

Example E8: Invention E8

Invention E8 was prepared using S10 and impregnated as E5. Then asubsequent impregnation was performed with 1,2-propanediol to reach 15wt. % in the final catalyst. The composition of the metal impregnateddried catalyst (dry base) was 23.6 wt. % MoO₃ and 4.1 wt. % NiO, 4.1 wt.% P₂O₅, 0.39 wt. % SiO₂, 14.4 wt. % TiO₂ and the rest is Al₂O₃.

TABLE 13 The effect of the addition of an organic in combination withTiO₂-containing support in the activity of NiMo catalysts in medium PULSD activity testing. mg RVA g_(CAT) db MoO₃ LHSV N HDN Example SupportAdditive Reactor Reactor HDN (ppm) r.o. 1 Comparative E1 S1 No organic0.746 200 4.0 76 100% Comparative E5 S1 No organic 0.715 197 76 100%Comparative E2 S10 No organic 0.876 204 41 154% Comparative E6 S10 Noorganic 0.854 209 47 146% Comparative E7 S1 1,2-propanediol 0.709 204 51135% Invention E8 S10 1,2-propanediol 0.876 230 7 307% S_(xy) 122

As can be observed in Table 13, the activity of Invention E8 is largerthan what can be expected based on the individual benefits ofTi-containing support (E2 and E6 without organic) and the use of1,2-propanediol as organic additive (E7 without Ti-support). To oursurprise, the combination of Ti-containing support and the use of1,2-propanediol as organic additive (Invention E8) show greater activityimprovement than individual effects of support (E2 and E6) or organic(E7), resulting in a very significant synergy factor (S_(xy)). Sincedata from different tests have been used, RVA HDN is calculatedaccording to a different reference: E2 and E8 are relative toComparative E1, while E6 and E7 are relative to Comparative E5.

Example E9: Comparative E9

Comparative E9 was prepared using S1 and impregnated as E5. Then asubsequent impregnation was performed with 3-hydroxybutyric acid toreach 15 wt. % in the final catalyst. The composition of the metalimpregnated dried catalyst (dry base) was as E5.

Example E10: Invention E10

Invention E10 was prepared using S10 and impregnated as E9. Thecomposition of the metal impregnated dried catalyst (dry base) was 23.6wt. % MoO₃ and 4.1 wt. % NiO, 4.1 wt. % P₂O₅, 0.39 wt. % SiO₂, 14.4 wt.% TiO₂ and the rest is Al₂O₃.

TABLE 14 The effect of the addition of an organic in combination withTiO₂-containing support in the activity of NiMo catalysts in medium PULSD activity testing. mg RVA g_(CAT) db MoO₃ LHSV N HDN Example SupportAdditive Reactor Reactor HDN (ppm) r.o. 1 Comparative E1 S1 No organic0.746 200 40 76 100% Comparative E5 S1 No organic 0.715 197 76 100%Comparative E2 S10 No organic 0.876 204 41 154% Comparative E6 S10 Noorganic 0.854 209 47 146% Comparative E9 S1 3-hydroxybutiric acid 0.731211 49 144% Invention E10 S10 3-hydroxybutiric acid 0.898 236 6 334%S_(xy) 140

As can be observed in Table 14, the activity of Invention E10 is largerthan the individual benefits of Ti-containing support (E2 and E6 withoutorganic) and the use of 1,2-propanediol as organic additive (E9 withoutTi-support). To our surprise, the combination of Ti-containing supportand the use of 3-hydroxybutiric acid as organic additive (Invention E10)show greater activity improvement than individual effects of support (E2and E6) or organic (E9). Since different LHSV have been used, RVA HDS iscalculated according to a different reference: E2 and E10 are relativeto Comparative E1, while E6 and E9 are relative to Comparative E5.

In ULSD applications, the removal of S to very low S-levels (<10 ppm) isthe main objective. As a result, HDS-activity at high conversion is themost important activity parameter. However, it is well known thatN-compounds inhibit the HDS reaction and removal of these molecules willgreatly enhance the HDS reaction rate towards 10 ppm S. Moreover, HDSkinetics are highly complex and the reaction order is a function ofconversion. HDN, on the other hand, is an apparent 1^(st) order reactionacross a large conversion range. For these reasons, we have chosen touse HDN activity as the most activity to determine the synergeticeffect.

Examples F: Effect of Co-Extruded Alumina Supports on the Activity ofNiMo Catalysts for ULSD Applications

The following examples illustrate the positive effect of TiO₂ additionin different ways as co-extruded supports on the activity of NiMocatalysts. The catalysts were prepared as described in examples F1-F3using the same method to apply metals and organic additives to thecatalysts and have a comparable volume loading of metals in the reactor.Approximately 0.9 ml of each of the catalysts was tested in amulti-reactor unit under medium pressure ultra-low sulfur dieselconditions. Table 15 shows the pre-sulfidation and test conditions andTable 16 shows the activity results.

TABLE 15 Pre-sulfiding and test (medium P ULSD) format used for activitytesting of NiMo catalysts from examples F. Pre-sulfiding conditions LHSVP H₂/oil Temperature Time Feed (1/hr) (bar) (Nl/l) (° C.) (hours) SpikedLGO 3 45 300 320 24 Testing conditions P H₂/oil Temperature Time @ Feed(bar) (Nl/l) (° C.) condition (days) SRGO with 1.1 wt. % 45 300 350 5 Sand 240 ppmN

Example F1: Comparative F1

Comparative F1 was prepared using support Sand impregnated with NiMoPaqueous solution and diethylene glycol. The NiMoP solution was preparedby dispersing of the required amount of NiCO₃ in water. The solution wasthen heated to 60° C. while stirring. Half of the required H₃PO₄ wasadded carefully to the solution and subsequently MoO₃ was added in smallportions. The solution was heated up to 92° C. to obtain a clearsolution. Then, the rest of the H₃PO₄ was added to the solution andwater was added to reach the concentration required for the desiredmetal loading. After cooling down, an amount of diethylene glycol toachieve 0.44 mol DEG per mol of metals (Mo+Ni) was added to thesolution. An amount of the final solution equivalent to fill 105% of thepore volume was used for impregnation, as is known for a person skilledin the art. The pore volume of the support was determined by a so-calledwater PV measurement in which the point of incipient wetness wasdetermined by addition of water to the carrier extrudates. Afterimpregnation, the extrudates were allowed to age for 1 hour in a closedvessel, after which drying was carried out at 120° C. for at least onehour. The composition of the metal impregnated dried catalyst (dry base)was 22.8 wt. % MoO₃ and 3.9 wt. % NiO, 6.8 wt. % P₂O₅, 0.66 wt. % SiO₂and the rest is Al₂O₃.

Example F2: Invention F2

Invention F2 was prepared using S15 and the same impregnation method asF1. The composition of the metal impregnated dried catalyst (dry base)was 22.7 wt. % MoO₃ and 3.8 wt. % NiO, 6.8 wt. % P₂O₅, 0.59 wt. % SiO₂,7.1 wt. % TiO₂ and the rest is Al₂O₃.

Example F3: Invention F3

Invention F4 was prepared using S13 and the same impregnation method asF1. The composition of the metal impregnated dried catalyst (dry base)was 23.2 wt. % MoO₃ and 3.9 wt. % NiO, 6.9 wt. % P₂O₅, 0.35 wt. % SiO₂,7.1 wt. % TiO₂ and the rest is Al₂O₃.

TABLE 16 The effect of the addition of an organic in combination withTiO₂-containing support in the activity of NiMo catalysts in medium PULSD activity. RVA mg RVA HDS g_(CAT) db MoO₃ LHSV N HDN LHSV S r.o.Example Support Reactor Reactor HDN (ppm) r.o. 1 HDS (ppm) 1.2Comparative F1 S14 0.847 193 4.0 28 100% 2.5 35 100% Invention F2 S150.928 211 14 132% 25 109% Invention F3 S13 0.795 185 18 120% 24 111%

As can be observed in Table 16, the catalysts with titania present inthe support show higher activity than Comparative catalyst F1 withouttitania when using the same metal preparation procedure and similarmetal loadings. The co-extruded titania and alumina support F2 showsvery similar activity as the precipitated sample (F3) shown in previousexamples when using diethylene glycol as organic additive.

Examples G: HC-PT Activity Data of NiMo Catalysts with Ribose as OrganicAdditive and TiO₂-Containing Supports

The following examples illustrate the positive effect of TiO₂ additionin the support and Ribose as organic additive on the activity of NiMocatalysts in HC-PT application. The catalysts were prepared as describedin examples G1-G4 using the same method to apply metals and organicadditives to the catalysts and have a comparable volume loading ofmetals in the reactor. Approximately 0.9 ml of each of the catalysts wastested in a multi-reactor unit under medium pressure ultra-low sulfurdiesel conditions. Table 17 shows the pre-sulfidation and testconditions and Table 18 shows the activity results.

TABLE 17 Pre-sulfiding and HC-PT test format used for activity testingof NiMo catalysts from examples G. Pre-sulfiding conditions P LHSVH₂/oil Temperature Time Feed (bar) (1/hr) (Nl/l) (° C.) (hours) SpikedLGO 45 3 300 320 24 Testing conditions P LHSV H₂/oil Temperature Time @Feed (bar) (1/hr) (Nl/l) (° C.) condition (days) VGO with 120 1.7 1000380 3 2.1 wt. % S and 1760 ppmN

Example G1: Comparative G1

Comparative G1 was a commercial NiMo catalyst with no titania in thesupport and no Ribose additive.

Example G2: Invention G2

Comparative G1 was prepared using support S16 and impregnated with NiMoPaqueous solution without organics. After that, 0.44 mol Ribose/molMetals were dissolved in water and impregnated in the previous sampleallowed to age for 2 hours. The final catalyst was dried in a staticoven at 100° C. overnight. The composition of the metal impregnateddried catalyst (dry base) was 27.7 wt. % MoO₃ and 5.0 wt. % NiO, 4.2 wt.% P₂O₅, 0.37 wt. % SiO₂, 3.5 wt. % TiO₂ and the rest is Al₂O₃.

Example G3: Invention G3

Invention G3 was prepared using S17 and the same impregnation method asG2. The composition of the metal impregnated dried catalyst (dry base)was 27.9 wt. % MoO₃ and 5.1 wt. % NiO, 4.2 wt. % P₂O₅, 0.39 wt. % SiO₂,6.8 wt. % TiO₂ and the rest is Al₂O₃.

Example G4: Invention G4

Invention G4 was prepared using S18 and the same impregnation method asG2. The composition of the metal impregnated dried catalyst (dry base)was 26.0 wt. % MoO₃ and 4.4 wt. % NiO, 3.9 wt. % P₂O₅, 0.40 wt. % SiO₂,13.6 wt. % TiO₂ and the rest is Al₂O₃.

TABLE 18 The NiMo catalysts activity in HC-PT testing for TiO₂ supportedRibose/NiMo catalysts from examples G (vs a commercial NiMo catalyst).g_(CAT) mg RVA db MoO₃ RVA HDS Re- Re- N HDN S r.o. Example Supportactor actor (ppm) r.o. 1 (ppm) 1.2 Comparative NiMo 0.748 232 72 100%198 100% G1 commercial catalyst Invention G2 S16 0.896 266 55 109% 153109% Invention G3 S17 0.886 265 27 131% 94 127% Invention G4 S18 0.899257 29 129% 103 123%

As can be observed in Table 16, the Invention examples with Ti-additionin the catalyst support (G2-G4) show significantly higher performancethan the Comparative G1 (no titania) example. It is clear that thesamples with 10 and 20 wt. % TiO₂ are better than the sample with 5 wt.% TiO₂ at similar metal loading.

Components referred to by chemical name or formula anywhere in thespecification or claims hereof, whether referred to in the singular orplural, are identified as they exist prior to coming into contact withanother substance referred to by chemical name or chemical type (e.g.,another component, a solvent, or etc.). It matters not what chemicalchanges, transformations and/or reactions, if any, take place in theresulting mixture or solution as such changes, transformations, and/orreactions are the natural result of bringing the specified componentstogether under the conditions called for pursuant to this disclosure.Thus the components are identified as ingredients to be brought togetherin connection with performing a desired operation or in forming adesired composition.

The invention may comprise, consist, or consist essentially of thematerials and/or procedures recited herein.

As used herein, the term “about” modifying the quantity of an ingredientin the compositions of the invention or employed in the methods of theinvention refers to variation in the numerical quantity that can occur,for example, through typical measuring and liquid handling proceduresused for making concentrates or use solutions in the real world; throughinadvertent error in these procedures; through differences in themanufacture, source, or purity of the ingredients employed to make thecompositions or carry out the methods; and the like. The term “about”also encompasses amounts that differ due to different equilibriumconditions for a composition resulting from a particular initialmixture. Whether or not modified by the term “about”, the claims includeequivalents to the quantities.

Except as may be expressly otherwise indicated, the article “a” or “an”if and as used herein is not intended to limit, and should not beconstrued as limiting, the description or a claim to a single element towhich the article refers. Rather, the article “a” or “an” if and as usedherein is intended to cover one or more such elements, unless the textexpressly indicates otherwise.

Each and every patent or other publication or published documentreferred to in any portion of this specification is incorporated in totointo this disclosure by reference, as if fully set forth herein.

This invention is susceptible to considerable variation in its practice.Therefore the foregoing description is not intended to limit, and shouldnot be construed as limiting, the invention to the particularexemplifications presented hereinabove.

The invention claimed is:
 1. A method of producing a catalyst, themethod comprising precipitating a titanium source with an aluminumsource, extruding the precipitate to form a titanium-containing carrierextrudate, drying and calcining the extrudate, and impregnating thecalcined extrudate with an organic additive, at least one Group VIBmetal source and/or at least one Group VIII metal source, the amount ofthe titanium source being sufficient so as to form a catalystcomposition at least having a titanium content in the range of about 1to about 60 wt. %, expressed as an oxide (TiO₂) based on the totalweight of the catalyst and has less than 1.0 wt. % silica expressed asan oxide (SiO₂) and based on the total weight of the catalyst; whereinthe precipitation comprises the steps of (a) simultaneous dosing ofsodium aluminate and aluminum sulfate to water at a fixed pH (b)re-slurrying the formed alumina filter cake in water (c) adding to thisslurry TiOSO₄ or titanium sulfate at a fixed pH>7 controlled by analkaline solution.
 2. A method of producing a catalyst, the methodcomprising precipitating a titanium source with an aluminum source,extruding the precipitate to form a titanium-containing carrierextrudate, drying and calcining the extrudate, and impregnating thecalcined extrudate with an organic additive, at least one Group VIBmetal source and/or at least one Group VIII metal source, the amount ofthe titanium source being sufficient so as to form a catalystcomposition at least having a titanium content in the range of about 1to about 60 wt. %, expressed as an oxide (TiO₂) based on the totalweight of the catalyst and has less than 1.0 wt. % silica expressed asan oxide (SiO₂) and based on the total weight of the catalyst; whereinthe aluminum source and the titanium source are mixed in one stream andsodium aluminate are dosed either simultaneously or subsequently towater at a pH>7.
 3. The method of claim 1 or 2 wherein the organicadditive is an organic compound selected from the group consisting oforganic compounds comprising at least two oxygen atoms and 2-10 carbonatoms, and the ethers, esters, acetals, acid chlorides, acid amides,oligomers or polymers thereof and the impregnation is performed in asingle step with a solution comprising an organic additive, at least oneGroup VIB metal source and/or at least one Group VIII metal source. 4.The method of claim 1 or 2 wherein the organic additive is an organiccompound selected from the group consisting of organic compoundscomprising at least two oxygen atoms and 2-10 carbon atoms, and theethers, esters, acetals, acid chlorides, acid amides, oligomers orpolymers thereof and the impregnation is performed in more than onestep, wherein the carrier is impregnated with a solution comprising atleast one Group VIB metal source and/or at least one Group VIII metalsource, followed by a step of impregnating the carrier with a solutioncomprising an organic additive.
 5. The method of claim 1 or 2 furthercomprising the titanium source being selected from the group consistingof titanyl sulfate, titanium sulfate, titanium alkoxide, orTitanium(IV)bis(ammonium lactato)dihydroxide.